Process for breaking petroleum emulsions employing certain amine-modified thermoplastic phenol-aldehyde resin salts



United States Patent PROCESS FOR BREAKING PETROLEUM EMUL- SIONSEMPLOYING CERTAIN AMlNE-MODI- FIED THERMOPLASTIC PHENOL-ALDEHYDE RESINSALTS Melvin De Groote, University City, Mo, assignor to PetroliteCorporation, Wilmington, DeL, a corporation of Delaware N 0 Drawing.Application January 2, 1953, Serial No. 329,486

18 Claims. (Cl. 252341) The present invention is a continuation-in-partof my two co-pending applications, Serial No. 288,746, filed May 19,1952, now abandoned, and Serial No. 296,087, filed June 27, 1952, now U.S. Patent 2,679,488.

My invention provides an economical and rapidprocess for resolvingpetroleum emulsions of the water-in-oil type, that are commonly referredto as cut-oil, roily oil, emulsified oil, etc., and which comprise finedroplets of naturally-occurring waters or brines dispersed in a more orless permanent state throughout the oil which constitutes the continuousphase of the emulsion.

It also provides an economical and rapid process for separatingemulsions which have been prepared under controlled conditions frommineral oil, such as crudeoil and relatively soft waters or Weak brines.Controlled emulsification and subsequent demulsification under theconditions just mentioned are of significant value in removingimpurities, particularly inorganic salts, from pipeline oil.

My aforementioned co-pending application, Serial No. 296,087, filed June27, 1952, is concerned with a process for breaking petroleum emulsionsof the water-in-oil type characterized by subjecting the emulsion to theaction of a demulsifier including certain amino resin condensatestherein described.

My present invention is concerned with demulsification which involvesthe use of the aforementioned amino resin condensate in the form of,agluconic acid salt, i. e.,a form in which all or part of the basicnitrogen atoms are neutralized with gluconic acid, i. e., converted intothe salt of gluconic acid.

Needless to say, all that is required is to prepare the amine resincondensates in the manner described inthe two aforementioned co-pendingapplications, and then neutralize with gluconic acid which, forpractical purposes is as simple as analogous inorganic reactions.

As far as the use of the herein described products goes for purpose ofresolution of petroleum emulsions of the water-in-oil type, Iparticularly prefer to use the gluconic acid salt of those members whichhave sufiicient hydrophile character to meet at least the test as setforth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Grooteet al. In said patent such test for emulsification using awater-insoluble solvent, generally xylene, is described as an index ofsurface activity.

The present invention involves the surface-activity of the gluconic acidsalts, i. e., eit-herwhere onlyone ,basic amino nitrogen atom isneutralized or where all basic amino nitrogen atoms are neutralized.Such gluconic acid salts may not necessarily be xylene-soluble. If suchcompounds are not xylene-soluble the obvious chemical equivalent orequivalent chemical test can be made by simply using some suitablesolvent, preferably a watersoluble solvent such as ethylene glycoldiethylether, or a low molal alcohol, or a mixture to dissolve theappropriate product being examined and then mix with the equal weight ofXylene, followed by addition of water. Such test is obviously the samefor the reason that there 2,771,444 Patented Nov. 20, 1956 "ice 2 willbe two phases on vigorous shaking and surface activity makes itspresence manifest. It is understood the reference in the hereto appendedclaims as to the use of xylene in the emulsification test includes suchobvious variant.

For convenience, what is said hereinafter will be divided into sixparts:

Part 1 is concerned with the general structure of the amine-modifiedresins which are converted into the gluconic acid salt;

Part 2 is concerned with the phenol-aldehyde resin which is subjected tomodification by condensation reaction to yield the amine-modified resin;

Part 3 is concerned with suitable basic amidines which may be employedin the preparation of the herein de-' scribed amine-modified resins;

Part 4 is concerned with the reactions involving the resin, the-amidine,and formaldehyde to produce the .specific products or compounds whichare neutralized subsequently with gluconic acid;

I Part 5 .isconcerned with the conversion of thebasic condensate intothe corresponding salt of gluconic acid;" 1

Part 6 is concerned with the resolution of petroleurri emulsions of thewater-in-oil type by means'oftlie previously described chemicalcompounds or reactions prodnets in the form of gluconic acid salts;

The compounds herein described and particularly useful asdemulsifyingagents are gluconic acid salts of the condensates generically describedabove and indetail inapplications Serial Nos. 288,746 and 296,087 towhich reference is made.

These resins may be exemplified by an idealized formula which may, inpart, bean "0ver-simplificatioi1 -in an effort to present certain resinstructure. Such formula would be the following: i l

in which R represents an aliphatic hydrocarbonsubstituent generallyhaving four and not over 18'carbon atoms but most preferably not over 14carbon atoms, and n generally is a small whole number varying from llto4. In the" resin structure it is shown as being derived fromformaldehyde although obviously other aldehydes are equallysatisfactory. The amine residue in the above.

depicted in the above formula is an over-simplification as far as'thering compound is concerned which is obvious by reference to a moreelaborate formula depicting" the actual structure of typical members ofthe grou'p, such as:

%N O H: C H3. 0

N C H2 CzH-1.NH. Cz'HnNH. CiflHas'Z-me'thyl,l-hexadecylaminoethylaminoethylimidazoliue V2-heptadecyl,l-methylaminoethyl tetrallydropyrimiditte The introductionof two'such ring compound radicals I intoa comparatively small resinmolecule, for instance,

one having 3 to 6 phenolic nuclei as specified, alters the product in anumber of ways. In the first place, a basic nitrogen atom, of course,adds a hydrophile'effect; in the second place, depending on the size ofthe radical R'," there may be a counterbalancing hydrophobe effect orone in which the hydrophobeeftect more than counterbalances thehydrophile effect of the nitrogen atom. Finally,in such cases where Rcontains one or more 7 oxygen atoms, another eflect is introduced,particularly another hydrophileeffect. In such instances where there arehydroxyl groups present, needless to say there is a further hydrophileeffectintroduced.

groups which are reactive to formaldehde, i. e., they are difunctionalfrom the standpoint of methylol-forming reactions. As is well known,although one may start 1 with difunctional phenols, and'depending on theprocedure employed, one may obtain cross-linking which indicates thatone or more of the phenolic nuclei have been converted from adifunctional radical to a trifunctional I radical, or 1n terms of theresin, the molecule as a whole has a methylol-forming reactivity greaterthan 2. Such shiftcan take place after the resin has been formed orduring resin formation. Briefly, an example is simply where analkylradical, such as methyl, ethyl, propyl, butyl, or the like, shiftsfrom an ortho position toa meta the like, and produce a homogeneousphase.

bility, particularly when employed as a reactant for preparation ofderivatives, is still important from the standpoint of manufacture ofthe condensation products themselves insofar that in the condensationprocess employed in preparing the compounds described subsequently indetail, there is no objection to the employing of a temperature abovethe boiling point of water. As a matter of fact, all the examplesincluded subsequently employ temperatures going up to 140 to 150 C.

What is said above deserves further amplification at this point for thereason that'it may shorten what is said subsequently in regard to theproduction of the herein described condensation products. Sinceformaldehyde generally is employed economically in an aqueous phase (30%to 40% solution, for example) it is necessary to have manufacturingprocedure which will allow reactions to take place at the interface ofthe two immiscible liquids, to wit, the formaldehyde solution and theresin solution, on the assumption that generally the amine will dissolvein one phase or the other. Although reactions of the kind hereindescribed will begin at least at comparatively'low temperatures, forinstance, 30 C., 40 C., or 50 0, yet I the reaction does not go tocompletion except by the use I of the higher temperatures. The use ofhigher temperatures means, of course, that the condensation productobtained at the end of the reaction must not be heatreactive. Of course,one can add an oxygenated solvent such as alcohol, dioxane, variousethers of glycols, or If this latter-procedure is employed in preparingthe herein described condensations it is purely a matter of convenience,

but whether it is or not, ultimately the temperature must still passwithin the zone indicated elsewhere, i. e., somewhere above the boilingpoint of water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to the procedureemployed in the process is not intended to limit the method or order inwhich the reactants are positionfor from a para position to a metaposition. 'For instance, in the case of phenol-aldehyde varnish resins,onecan prepare at least some in which the resins, instead of having onlytwo points of reaction can have three, and

a possibly more points of reaction, with formaldehyde, or

any other reactant which tends to form a methylol or substitutedmethylol group.

The resins herein employed are soluble in a non-oxygenated hydrocarbonsolvent, such as benzene or xylene. The resins herein employed as rawmaterials must be comparatively low molal products having on the average3to 6 nuclei .per resin molecule. p

The condensation products here obtained, whether in the? form of thefree base or the salt, do not go over to the insoluble stage on heating.The condensation product obtained according to the present invention isheat stable '7 v and, in fact, one of its outstanding qualities is thatit can be subjected to oxyalkylation, particularly oxyethylation oroxypropylation, underconventional conditions,

e., presence of analkaline catalyst,' for example, but in any event at atemperature above 100 C. without becoming an insoluble mass.

What has been said prev ionslyin regard to heat staadded, commingled orreacted. The procedure has been referred to as a condensation processfor obvious reasons.

As pointed out elsewhere it is my .preferencelto dissolve methylolgroups attached to the phenolic nuclei which, in turn, react with theamine.

It would be immaterial, of course, if the formaldehyde reacted with theamine so as to introduce a methylol group attached to nitrogen which, inturn, would react with the resin molecule.

Also, it would be immaterial if both types of compounds were formedwhich reacted with each other with the evolution of a mole offormaldehyde available for further reaction. Furthermore, a reactioncould take place in which three difierent molecules are simultaneouslyinvolved although, for theoretical reasons, that is less likely. What issaid herein in this respect is simply by way of explanation to avoid anylimitation in regard to the appended claims. PART 2 It, is well knownthat one can readily purchase on the open market, or prepare, fusible,organic solventsoluble, water-insoluble resin polymers of a compositionH H OH H r H1 R R V n R or 12. units, particularly when the resinissubjected, to

heating under a vacuum as described in the literature. A limitedsubgenus is in the instance of low molecular weight polymers where thetotalnumber of phenol nuclei varies from 3 to 6, i. .e., n varies from 1to 4; R represents an aliphatic hydrocarbon substituent, generally analkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl,hexyl, decyl ordodecyl radical. Where the divalent bridge radical isshown as being derived from formaldehyde it may, of course, be derivedfrom any other reactive aldehyde having '8 carbon atoms or less.

The resins herein employed as raw materials must be soluble in anonoxygenated solvent, such as benzene or xylene. This presents noproblem insofar that all that is required is to make a solubility teston commercially available resins, or else prepare-resins which arexyleneor benzene-soluble as described in aforementioned U. S. Patent No.2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to DeGroote; and Keiser.

If one selected a resin of theukind just described previously andreacted approximatelyrone mole of the ,1'6Sil1 with two moles offormaldehyde and two moles of a basic nonhydroxylated secondary amine asspecified, following the same idealized over-simplification previouslyreferred to, the resultant product might be illustrated 'The basic aminemay be designated thus:

subject to what has been said previously as to the presence of asubstituted imidazoline or a substituted tetrahydropyrimidine radicalhaving at least one basic secondary amine radical present and that thering compound, or rather the two occurrences of R jointly with n, befree from a primary amine radical. However, if one attempts toincorporate into the formula RI HN a structure such as a substitutedimidazoline or substituted tetrahydropyrimidine such as the following:

then one becomes involved in added difficulties in presenting an overallpicture. Thus, for sake of simplicity the ring compound having thereactive secondary amino group will be depicted as subject to thelimitation and explanation previously noted.

In conducting reactions of this kind one does not necessarilyv obtain ahundredper. cent yield forpbvrous reasons. Certain side reactions maytake place. For instance, 2 moles of amine may combine with one moleof'the aldehyde, or only one mole of -the amine may .combine with theresin molecule, or even to a very slight extent, if atall, 2 resin unitsmay combine without any amine in the reaction product, as indicated inthe following formulas:

As has been pointed out previously, as far as the resin unit goes onecan use a mole of aldehyde other than formaldehyde, such asacetaldehyde, propionaldehydc or butyraldehyde. The resin unit may beexemplified thus:

0 H O H "I O O ur O n/ R R 1L R is preferable that the resins employedbe substantially neutral. In other words, if. prepared by using a strongacid as a catalyst, such strong acid should be neutralized. Similarly,if a strong base is used as a catalyst it is preferable that. the basebe neutralized although I have found that sometimes the reactiondescribed proceeded more rapidly in the presence of a small amount of afree base.

The amount may be as small as a 200th of a percentand as much as a few10ths of a percent. Sometimes moderate increase in caustic soda andcaustic pot-ash may be used. However, the most desirable procedure inpractically every case is to have therresin neutral.

In preparing resins one does: not get a single polymer, i.e., one havingjust 3 units, or just 4 units, or just 5 units, or just 6 units, etc. Itis usually a mixture; for instance, one approximating 4 phenolic nucleiwill have some trimer' and pentamerp-resent. Thus, the molecular weightmay be such that it corresponds to a fractional value for n as, forexample, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no reason for usingother than those which are lowest in price and most readily availablecommercially. For purposes of convenience suitable resins arecharacterized in the following table:

w w w m w e n .1 l m a e m m m m 1 m 1 i u m M H 0 m H m 1 l O 7 .1 1 d2 d C M Z 1 m C .1 H .1 O 5 a C .1 m 0 m H 2 .1 C 2 8 1 H N .m H H y H n.m y m m o m o v. o a mm mm 11 o a M M H H a 2 y H v. n 0 N do e 4.2.,own w mm nm .1 H I 2 2 H e C m r C a 2 mN N mm Nm m inn mm W w m N N cmnnNwm m m n M m m C o a o O m l ll 4 I. 1 C 1 2 v. H m I C H y N Nllnu X2 d 0 1 0 m m m N Nlo .1 w a m c w m M C H r M 1 t t 1 L h s y 1 .m 1 em 2 5 0 5 0 5 0 5 0 1 1 2 2 3 3 4 h h m. 5 .55 4704640000 000 000 000 d2 22595 56 7 85 201 868 536 30 4 0 mfiwamem 6 55m 06 280 awm m W %%M%%%%1 MNM mw WW mfiwmmwmflwfl m mwfl WHH OHIOJDD L. LLIILL, LLI: 1. 1 111L. LLLLL. .L. M m 5 55556 555 555 552 228885555 550 000 000 n 3 3 .34d id nmdflLllL LLZ.

TABLE I C H| Ehb/ 2-heptadecy1,1methylaminoethyl tetrahydropyrimidine H.l |T.CzH .NH0 C-CH;

12 1- (N-dodecyl -acetamidoethylaminoethylimidazoline N CH-CHa N CHCHa4,5-dimethy1imidazo1ine N -C Hz I CH2 i Ou iz.NH.Cn 251-dodecylaminohexylimidazoline .NH.C2H4. 0 0 511 5 N-OH;

N-GHz H.C\ l III-C 0'2 CuHas-C I 2-heptadecy1,

HC\N /NCH2 H.C\

III-CH1 Co n 1-stear0yloxyethylnminohexylimidazoline CnHss-O PART 3 Theexpression cyclic amidines is employed in its usual sense to indicatering compounds in which there are present either 5 members or 6 members,and having 2 plemented by either two additional carbon atoms or threeadditional carbon atoms completing the ring. All the carbon atoms may besubstituted. The nitrogen atom of the ring involving two monovalentlinkages may be substituted. Needless to say, these compounds includemembers in which the substituents also may have one or more nitrogenatoms, either in the form of amino nitrogen atoms or in the form ofacylated nitrogen atoms. Reference is made to application Serial No.296,087 for detailed description of suitable amidines and theirpreparation.

Examples selected include the following:

2-undecy1imidazo1ine Z-heptadecylimidazoline nitrogen atoms separated bya single carbon atom sup-4-methyl,2-dodecy1,1-methylaminoethylaminoethyl vtetrahydropyrimidine,As has been pointed out previously, the reactants herein iemployed mayhave two substituted imidazoline rings ortwosubstituted'tetrahydropyrimidinerings. Suchcompounds are illustrated bythe following formula:

As to compounds having'a tertiaryv amine radical, it is' obvious thatone can employ derivatives of 'polyamines in which the terminal groupsare ,unsymmetrically alkylin which R representsa small alkyl radicalsuch as methyl,

ethyl, propyl, etc., and n represents a small whole number greater thanunitysuch as 2, 3 or 4.

Ringcompounds, such as substituted imidazolines, may be reacted with asubstantial amount of alkylene oxide as-.noted in the precedingparagraph and then .a second- :ary amino groupintroduced by. two steps;first, reaction with an ethylene imine, and second, reaction withanother mole of the oxide, or with analkylatingagent such asdimethylsulfate, benzyl chloride, a low molal ester of asulfonic acid, an alkylbromide, etc.

Other suitable means may be employed to eliminate aterminal primaryamino radical. If there is additionally a basic secondary amino radicalpresent then the primary amino radicalcan be subjected to acylationvnotwithstanding the factthattthe surviving amino group. has nosignificant basicity. As a rule acylation takes place at thetermina'l'primaryamino group rather. than at the secondary amino-group,thus one can employ a compound such as CzH4.NH. C2H4.NH2

.2-heptadecyLl-diethylenediaminoimidazoline "and" subject" it toacylation so as to obtain,-"for example,

acetylated 2-heptadecyl,1-diethylenediaminoimidazolingof the followingstructure: r v I In the foregoing examplesthere is present a sizablehydrophobe group, for instance, heptadecyl groups, pentadecyl groups,octyl groups, nonyl groups, etc. etc.

One'can obtain all these comparable derivatives from low molal acids,such asacetic, propionic, butyric, valeric, etc. Similarly, one canemploy hydroxy acids such as glycolid acids, lactic acid, etc. Over andabove this, one may employ acids which introduce a very distincthydrophobe effect.

Examples of decreased hydrophobe character are exemplified by2-methylimidazoline, 2-propylimidazoline, and 2-butylimidazoline, of thefollowing structures:

N-OH,

PART 4 The products obtained by the herein described processes representcogeneric mixtures which are the result of a condensation reaction orreactions. Since the, resinmolecule cannot be defined satisfactorily byformula, although it may be so illustrated in an idealizedsimplification, it is diflicult to actually'depict the final product ofthe cogeneric mixture except in terms'of the process itself. Referenceis made to application Serial No. 296,087 for a detailed description ofthe reaction and the factors .involved. p

Little more need be said as to the, actual procedure employed for'thepreparation of theherein described 11 condensation products. Thefollowing example'will ,serve by way of illustration:

Example lb The phenol-aldehyde resin is the one that has been identifiedpreviously as Example 2a. It was obtained from a para-tertiarybutylphenol and formaldehyde. The resin was prepared using an acidcatalyst which was completely neutralized at the end of the reaction.The molecular weight of'the resin was 882.5. This corresponded to anaverage of about 3 /2 phenolic nuclei, as the value for n which excludesthe 2 external nuclei, i. e., the resin was largely a mixture having 3nuclei and 4 nuclei excluding the 2 external nuclei, or 5 and 6 overallnuclei.

color.

12 that in Table II following there are a large number of added examplesillustrating the same procedure. In each case the initial mixture wasstirred and held at a fairly low temperature (30 to 40 C.) for a periodof several hours. Then refluxing was employed until the odor offormaldehyde disappeared. After the odor of formaldehyde disappeared thephase-separating trap was employed to separate out all the water, boththe solution and condensation. After all the water had been separatedenough 1'0 xylene was taken out to have the final product reflux forseveral hours somewhere in the range of 145 to 150 C., or thereabouts.Usually the mixture yielded a clear solution by the time the bulk of thewater, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24examples in Table I1.

TABLE II Strength of Reac- Reae- Max. Ex Resin Amt., Amine used Amt. offormaldehyde Solvent used tion tion distill. No used grs. amine, soln.and and amt. temp., time temp.,

grams amt. 0. (hrs.) C.

612 37%, 162 g... Xylene, 600 g -25 148 306 37%, 81 g Xylene, 450 g21-23 24 145 306 o Xylene, 600 g 20-22 28 150 281 30%, 100 g Xylene, 400g.... 22-24 28 148 281 do Xylene, 450 g 21-28 30 148 281 37%, 81 gXylene, 600 gm- 21-25 26 146 394 do Xylene, 400 g. 23-28 26 147 394 doXylene, 450 g. 22-26 26 146 394 do Xylene, 600 55.... 21-25 38 160 37930%, 100 g Xylene, 450 g 20-24 36 149 379 do Xylene, 500 g. 21-22 24 142379 do Xylene, 650 gm. 20-21 26 145 395 38%, 81 g. Xylene, 425 g 22-2828 146 395 37%, 81 gm- Xylene, 450 g 23-30 27 160 395 do Xylene, 550 g20-24 29 147 99 do. Xylene, 440 g 20-21 30 8 99 d Xylene, 480 g 21-26 32146 99 Xylene, 600 g 21-23 26 147 113 Xylene, 500 g 21-32 29 150 113 .doXylene, 550 g 21-23 37 150 126 do Xylene, 440 g 20-22 30 150 126 doXylene, 600 g 20-25 36 149 126 30%, 50 g. Xylene, 400 g 20-24 32 152 882grams of the resin identified as 2a, preceding, were powdered and mixedwith a somewhat lesser amount of xylene, i. e., 600 grams. The mixturewas refluxed until solution was complete. It was then adjusted toapproximately C. and 612 grams of 2-oleylimidazoline, previously shownin a structural formula as ring compound (3), were added. The mixturewas stirred vigorously and formaldehyde added slowly. In this particularcase the formaldehyde used was a 37% solution and 162 grams were addedin approximately 3 hours. The mixture was stirred vigorously and keptwithin a range of approximately 40 to 44 C., for about 16 /2 hours. Atthe end of this time it was refluxed, using a phase-separating trap anda small amountv of aqueous distillate withdrawn from time to time.formaldehyde was noted. Any unreacted formaldehyde seemed to disappearin approximately three hours after refluxing started. As soon as theodor of formaldehyde was no longer detectible the phase-separating trapwas set so as to eliminate all the water oflsolution and reaction. Afterthe water was eliminated part of the xylene was removed until thetemperature reached approximately 148 C. The mass was kept at thishigher temperature for 3 or 4 hours. During this time any additionalwater, which was probably water of reaction which had formed, waseliminated by means of the trap. The residual xylene was permitted tostay in the cogeneric mixture. A small amount of thesample was heated ona water bath to remove the excess xylene. The residual material was darkred "in color and had the, consistency of a thick sticky fluid or tackyresin. Theoverallreaction time was approximately 30 hours. '-In otherexamples it varied from as little as 24 hours up to approximately 38hours. The time can be reduced by cutting the low temperature period toapproximately 3 tol6 hours.- Note The presence of unreacted The aminenumbers referred to are the ring compounds identified previously bynumber in Part 3.

PART 5 The conversion of the basic condensate of the kind previouslydescribed into the corresponding salt of gluconic acid is a simpleoperation since it is nothing more nor less than neutralization. Thecondensates invariably contain more than two basic nitrogen atoms.One'can neutralizeeither one, or more, basic'nitrogen.atoms.-

Gluconic acid is available as a 50% solution. Dehydration causesdecomposition. This is not true of the salts, atleast not of the saltsof the herein described condensates. Such salts appear to be stable, orstable for all practical purposes, at temperatures slightly above theboilingpoint ofwater and perhapsat temperatures as high as 150 C. orthereabouts. 4 a 1 'For reasons pointed out previously, itisfrriostconvenient to handle the condensate as 'a'solution, generally asolutionin an inexpensive solvent, such 'as' benzene, xylene, anaromatic petroleum solvent, or the like. -A number 0f thecondensatespreviouslydescribed have been prepared in 50% solution as noted. Addingthe calculated stoichiometric'amount of 50% gluconic acid,

"calculated on the basis of the theoreticalbasic nitrogen atoms present,forms such salt which, in many instances tory'funnel. If there isseparation of an aqueous phase, the aqueous phase is discarded and thesolution can be brought back to a predetermined concentration by theaddition of a hydrocarbon solvent, such as xylene, or by the addition ofan alcohol, such as methyl, ethyl, or propyl alcohol; or, if need by,one can employ a bridge solvent having hydrotropic properties in case ofthe diethylether of ethyleneglycol, or similar solvents.

The gluconic salts can be obtained in non-aqueous solution by using aslightly modified procedure. The procedure depends on the fact that thephase-separating trap can be used but it is preferable to stay below 150C. so as to avoid any possible decomposition.

The xylene solution of the condensate, as previously described, issubjected to vacuum distillation so as to remove about one-half thexylene. Approximately twothirds of the xylene removed is replaced bybenzene. This mixed solvent combination is subjected to refluxing actionunder a condenser with a phase-separating trap. With the distillationpoint adjusted so as to be somewhere between 110 to 135 C. the mixtureis refluxed and the Water separated. If it is not within this range morebenzene is added or, if need be, a little more xylene is added to bringit within the range. By this method the phaseseparating trap eliminatesthe water. The temperature at all times is left below 140 C. At the endof the separation a suitable amount of solvent is added, or eliminated,by distillation so as to yield a solution of predeterminedconcentration, for instance, 50%.

Using a somewhat similar procedure one can obtain the solvent-freematerial by merely subjecting the xylene solution of the condensate tovacuum distillation so as to remove all the xylene. The condensateitself is perfectly stable at 150 C. or thereabouts and, thus, there isno particular danger of degradation involved in this step. Thesolvent-free material is then dissolved in benzene instead of xylene andwater eliminated in the manner {previously described. The benzene iseliminated by vacuum distillation in such a way that the temperaturenever gets above 135 C. or 140 C. Actually, with care the solutionpreviously described, to Wit, the xylenebenzene solution, also can beremoved without decomposition.

An examination of the basic cyclic amidines employed indicates there maybe present at least three sub-genera. One sub-genera includes the typein which there is present a residual secondary amino group; anothersub-genera includes the type in which there is present a hydroxyl group,such as an ethanol group; and a third sub-genera contains both thesereactive groups. When such products are neutralized, particularly whenneutralization is complete, it

becomes apparent that one has amaterial whichwin one way, is analogousto triethanolamine oleate; or, for that matter, triethanolaminegluconate. In another way the analogy is similar to diethanolamineoleate'or diethanolamine gluconate. If diethanolamine oleate isheatedfit can be converted into oleyl diethanolamine, i. e.,,:involvingan ester linkage. Similarly, if diethanolamine oleate is heated one canform the corresponding amide or perhaps under certain conditions, thecorresponding ester. Obviously, esters can invariably and inevitablyform in regard to the completely neutralized productand even in somecases in regard to the partially neutralized product. This is, ofcourse, assuming that appropriate conditions of reaction are selected.In other instances where there is a residual secondary amine radical onemay form amides or, for that matter mixtures of both amidm and esters.For this reason previous reference. to decomposition must be construedto mean not only decom position in the sense that degradation or innerethers are formed, but also in the sense that an entirely new andvaluable compound, or compounds, may be formed. Such reactions, ofcourse, form water as a by.-'product regardless of whether amidificationor esterification is involved.

Example 10 This salt was made from condensate Example 1b. Example 1b, inturn, was made from Resin 2a and Amine 3 previously described in Part 3,preceding. 882 grams of the resinwere dissolved in about 600 grams ofxylene and reacted with 612 grams of the cyclic amidine previouslyidentified as Amine 3, along with 162 grams of 37% formaldehyde. Allthis has been described previously. Theweightof the condensate on asolvent-freebasis-was 1518 grams. This represented approximately 53grams of basic nitrogen subject'to'what is said in the note followingTable 'III which, in turn, immediately follows the present text.

To the above mixture, with constant stirring, there were added 1480grams of 50% gluconicacid. The mixture was stirred for one hour. Thissolution was poured into'a separatory'funnel or syphon arrangement-andallowed to stand for'abouttwo" daysat 40 C. There was atthe most aslight separation-of insoluble material at the bottom of theseparato'ry'funnel. This was withdrawn and grams of isopropyl alcoholadded and enough xylene to bring the final product-to approximately'a50% soluv TABLE III Condensate in turn derived from- Salt formation SaltSalt from Wt. of Theo- Final ex. eon- Amt. 37% eondenretieal 50% wt. ad-No. den- Resin Amt. sol- Amine iormsate on basic glu- 'justed to sateNo. resin, Solvent vent, Amine used 1 used, aldesolventnitroconicapprox. No. gms. gms. gms. hyde, free gen, acid, 50% salt,

gins. 1 basis, gms. 3 girls. 50% so1v.,

gms. gms.

612 162 1, 518 53 1, 480 4, 516 306 81 798 27 720 2,316 306 81 951 27720 2, 622 281 2 100 734 38 1, 065 2, 533 281 2 100 773 38 1, 065 2, 571281 81 826 38 1, 065 2, 717 394 81 847 42 1, 2, 869 394 81 886 42 1, 1752, 947 394 81 l, 039 42 1, 175 3, 253 395 2 100 880 42 1, 175 2, 935 3951 100 916 42 1, 175 3, 007 395 2 100 1, 069 42 1, 175 3, 313 612 162 1,51s 27 720 3,756 281 2 100 734 19 535 2,003 Amine 13 395 3 100 880 21585 2, 345

5 30% formaldehyde. 3 See text following.

PART 6 10 Conventional demulsi-fying agents employed in the treatment ofoil field emulsions are used as such, or after dilution with anysuitable solvent, such as water, petroleum hydrocarbons, such asbenzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc.Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethylalcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexylalcohol, octyl alcohol, etc;, may be employed as diluents. Miscellaneoussolvents'such as pine oil, carbon tetrachloride, sulfur dioxide extractobtained in the refining of petroleum, etc.,,may be employed asdiluents. Similarly, the material or materials employed as thedemulsifying agent of my process may be admixed'wi-th one or more of thesolvents customarily used in connection with conventional demul'sifyingagents. Moreover, said material or material-s may be used alone or inadmixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in awater-soluble form, or in an oil-soluble form, or in a form exhibitingboth oiland water-solu- .bility. Sometimes they may be used in a formwhich exhibits relatively limited oil-solubility. However, since i suchreagents are frequently used in a ratio oil to 10,000

01' 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or

1 to 50,000 as in desalting practice, such an apparent insolubility inoil and water is not significant because said reagents undoubtedly havesolubility within such concentrations. This same fact is true in regardto the material or materials employed as the demulsifying agent of myprocess.

In practicing the present process, the treating or demulsifying agent isused in the conventional way, well known to the art, described, forexample, in Patent 2,626,929, dated January 27, 1953, Part 3, andreference is made thereto for a description of conventional proceduresof demulsifying, including batch, continuous, and down-'the-holedemulsification, the process essentially involving introducing a smallamount of demulsifier into a large amount of emulsion with adequateadmixture with or without the application of heat, and allowing themixture to stratify.

As noted above, the products herein described may be used not only indiluted form, but also may be used .ad-' 5 mixed with some otherchemical demulsifier. A mixture which illustrates such combination isthe following:

Gluconic acid salt, for example, the product of Example 1c, 20%;

The above proportions are all weight percents. I

Having thus described my invention what I claim as" new and desire tosecure by Letters Patent, is: v:1. A process for breaking petroleumemulsions of the water-in-oil type characterized by subjecting theemulsion f to the action of a demulsifier including the gluconic acidsalts of the basic products obtained in turn in the process ofcondensing (a) an oxyalkylation-suscept-ible, fusible,

non-oxygenated organic solvent-soluble, water-insoluble, low-stagephenol-aldehyde resin having an average molec-. ular weightcorresponding to at least 3 and not over 6 phenolic nuclei per resinmolecule; said resin being difunctional only in regard tomethylol-forming reactivity; said resin being derived by reactionbetween a dif-unctional monohydric phenol and an aldehyde having notover 8 carbon atoms and reactive toward said phenol; said resin beingformed in the substantial absence of trifunctional phenols; said phenolbeing of the formula in which R is an aliphatic hydrocarbon radicalhaving at least 4 and not more than 24 carbon atoms and substituted inthe 2,4,6 position; (b) cyclic amidines selected from the classconsisting of substituted imidazolines and substitutedtetra-hydropyrimidines in which there is present at least one basicsecondary amino radical and characterized by freedom from any primaryamino radical; and (0) formaldehyde; said condensation reaction beingconducted at a temperature sufficiently high to eliminate water andbelow the pyrolytic point of the reactants and resultants of reaction;and with the proviso that the resinous, condensation product resultingfrom the process be heat-stable. i 2. A process for breaking petroleumemulsions of the water-in-oil type characterized by subjecting theemulsion to the action of a demulsifier including the gluconic acidsalts of the basic products obtained in turn in the process ofcondensing (a) 'an oxyalkylation-susceptible, fusible, non-oxygenatedorganic solvent-soluble, water-insoluble, low-stage phenol-aldehyderesin having an average molecular weight corresponding to at least 3 andnot over 6 phenolic nuclei per resin molecule; said resin beingdifunctional only in regard to methylol-forming reactivity;

said resin being derived by reaction between a difunc-- tionalmonohydric phenol and an aldehyde having not over 8 carbonatoms andreactive toward said phenol; said resin being formed in the substantialabsence of trifunctional phenols; saidphenol being of the formula inwhich R is an aliphatic hydrocarbon radical having at least 4 and notmore than 24 carbon atoms and substituted in the 2,4,6 position; (b)cyclic amidines selected from the class consisting of substitutedimidazolines and substituted tetrahydropyrimidines in which there ispresent at least one basic secondary amino radical and characterized byfreedom from any primary amino radical; and (0) formaldehyde; saidcondensation reaction being conducted at a temperature sufiiciently highto eliminate water and below the pyrolytic point of the reactants andresultants of reaction; with the added proviso that the condensationreaction be conducted so as to produce a significant portion of theresultant in which each of the three reactants have contributed part ofthe ultimate molecule; and with the further proviso that the resinouscondensation product resulting from the process be heatstable.

3. A processiorbreaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding thejgluconic acid salts of the basic products obtained in turnin the process of condensing (a) an oxyalkylatioii-susceptible, fusible,non-oxygenated organic solvent-soluble, water-insoluble,low-stage'phenokaldehyde resin having an average molecular weightcorresponding to at least'3 and not over 6 phenolic nuclei per resinmolecule; said resin being di- 1 7 functional only in regard tomethylol-forming reactivity; said resin being derived by reactionbetween a difunctiona1 monohydric phenol and an aldehyde having not over8 carbon atoms and reactive toward said phenol; said resin being formedin the substantial absence of trir'unctional phenols; said phenol beingof the formula in which R is an aliphatic hydrocarbon radical having atleast 4 and not more than 24 carbon atoms and substituted in the 2,4,6positions; (b) cyclic amidines selected from the class consisting ofsubstituted imidazolines and substituted tetrahydropyrimidines in whichthere is present at least one basic secondary amino radical andcharacterized by freedom from any primary amino radical; and (c)formaldehyde; said condensation reaction being conducted at atemperature sufficiently high to eliminate water and below the pyrolyticpoint of the reactants and resultants of reaction, with the proviso thatthe condensation reaction be conducted so as to produce a significantportion of the resultant in which each of the three reactants havecontributed part of the ultimate molecule by virtue of aformaldehyde-derived methylene bridge connecting the amino nitrogen atomwith a resin molecule; and with the further proviso that the resinouscondensation product resulting from the 'process be heat-stable.

4. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the gluconic acid salts of the basic products obtained in turnin the process of condensing (a) an oXyalkylation-susceptible, fusible,non-oxygenated organic solvent-soluble, waterinsoluble, low-stagephenol-aldehyde resin having an av erage molecular weight correspondingto at least 3 and not over 6 phenolic nuclei per resin molecule; saidresin being difunctional only in regard to methylol-forming reactivity;said resin being derived by reaction between a difunctional monohydricphenol and an aldehyde having not over 8 carbon atoms and reactivetoward said phenol; said resin being formed in the substantial absenceof trifunctional phenols; said phenol being of the formula in which R isan aliphatic hydrocarbon radical having at least 4 and not more than 24carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidinesselected from the class consisting of substituted imidazolines andsubstituted tetrahydropyrimidines in which there is prescut at least onebasic secondary amino radical and characterized by freedom from anyprimary amino radical; and (c) formaldehyde; said condensation reactionbeing conducted at a temperature sufliciently high to eliminate waterand below the pyrolytic point of the reactants and resultants ofreaction; with the proviso that the condensation reaction be conductedso as to produce a significant portion of the resultant in which each ofthe three reactants have contributed part of the ultimate molecule byvirtue of a formaldehyde-derived methylene bridge connecting the aminonitrogen atom with a resin molecule; with the further proviso that themolar ratio of reactants be approximately 1,2 and 2 respectively; andwith the final proviso that the resinous condensation product resultingfrom the process be heat-stable.

5. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the gluconic acid salts of the basic products obtained in turnin the I8 process of condensing (a an oxyalkylation-susceptible,fusible, non-oxygenated organic solvent-solublel water insoluble,low-stage phenol-aldehyde resin havinganiaw' erage molecular weightcorresponding to at least 3 and not over 6 phenolic nuclei resinmolecule; said resin being difunctional only in regard tomethylol-formingireactiv 1 ity; said resin being derived by reactionbetween a difunctional monohydric phenol and an aldehyde having it notover 8 carbon atoms and reactive toward said phenol; said resin beingformed in the substantial absence of trifunctional phenols; said phenolbeing of the formula in which R is an aliphatic hydrocarbon radicalhaving at least 4 and not more than 24-carbon atoms and sub: v

stituted in the 2,4,6 position; (b) cyclic amidines selected from theclass consisting of'substituted imidazolines and substitutedtetrahydropyrimidines in which there is present at least one basicsecondary amino radical and characterized by freedom from any primaryamino radical; and

(c) formaldehyde; said condensation reaction being conducted at atemperature sufliciently high to eliminate water and below thepyrolyticpoint of the reactants and resultants of reaction, with the proviso thatthe condensation reaction be conducted so as to produce a significantportion of the resultant in which each of the three reactants havecontributed part of the ultimate molecule by virtue of afornialdehyde-derived methylene bridge ,7

connecting the amino nitrogen atom with a resin molecule; with the addedproviso that the'molar ratio of reactants be approximately 1,2-and 2respectively; with the further proviso that said procedure involve theuse of a solvent; and with the final proviso that the resinous con-'densation product resulting from the process be heatstable.

6. A process for breaking petroleum emulsions of the Water-in-oil *typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the gluconic acid salts of the basic products obtained in turnin the process of condensing (a) an oxyethylation-susceptible, fusible,

non-oxygenated organic solvent-soluble, Water-insoluble, low-stagephenol-formaldehyde resin having an averagemolecular weightcorresponding to at least 3 andnot over 6 phenolic nuclei per resinmolecule; said resin-being difunctional only in regard tomethylol-forming reactivity; said resin being derived by reactionbetween a difunctional monohydric phenol and formaldehyde; said resinbeing formed in the substantial absence of trifunctional phenols; saidphenol being of the formula resultants of reaction, with the provisothat the condense- I tion reaction be conducted soasto produce asignificant portion of the resultant in which each of the threereactants have contributed part of the ultimate molecule by j virtue ofa formaldehyde-derived methylene bridge connecting the amino nitrogenatom with a resin molecule; with the added proviso that the molar ratioof reactants be approximately 1,2 and 2,;respectively; with the furtherproviso that said procedure involve the use of a solvent;

and with the-final provisothat the resinous c'ondensation productresulting from the process be heat-stable;

f "saltsof the basic products Obtained in turn in the process ofcondensing '(a) an oxyethylation-susceptible, fusible,

non-oxygenated organic solvent-soluble, water-insoluble,

low-stage phenol-formaldehyde resin having an average 7 molecular weightcorresponding to atleast 3 and not over 6 phenolic nuclei per resinmolecule; said resin being difunctional only inregard tomethylol-forming reactivity;

if said resin being derived by reaction between a difunctionalmonohydric phenol and formaldehyde; said resin being formedin thesubstantial absence of trifunctional phenols; said phenol being of theformula in which R is an aliphatic hydrocarbon radicalihaving at least 4and not more than 14 carbon atoms and substituted in the 2,4,6 position;(b) cyclic amidines selected from the'class consisting of substitutedimidazolines and substituted tetrah'ydropyrimidines in which there ispresent at least one basic secondary amino radical and characterized byfreedom from -any primary amino radical; and (c)'formaldehyde; saidcondensation reaction being conducted at a temperature sufliciently highto eliminate water and below the pyrolytic point of the reactants andresultants of reaction, with the proviso that the condensati=on reactionbe conducted so as to produce a significant portion of the resultantinwhich each of the three reactants have contributed part of theultimate molecule by virtue of a formaldehyde-derived methylene bridgeconnecting the amino nitrogen atom with a resin molecule; with the addedproviso that the molar ratio of reactants be approximately 1,2 and 2,respectively; with the further proviso that said procedure involve theuse of a solvent; and with the final proviso that the resinouscondensation product resulting from the process be heat-stable.

8. A process 'for breaking petroleum emulsion of the water-in-oil typejcharacterized by subjecting the emulsion to the action of a demulsifierincluding the gluconic acid I salts of the basic products obtained inturn in the process of condensing (a) an oxyethylation-susceptible,fusible,

non-oxygenated organic solvent-soluble, Water-insoluble, low-stagephenol-formaldehyde resinhaving an average molecular weightcorresponding to at least 3 and not over 6 phenolic nuclei per resinmolecule; said resin being difunctional only in regard tomethylol-forming reactivity; vsaid resin being derived by reactionbetween in which R is an aliphatic hydrocarbon radical having at least 4and not more than 14 carbon atoms and substituted in the 2,4,6 position;(b) cyclic amidines selected from the class consisting of substitutedimidazolines and substituted tetrahydropyrimidinesin which there ispresent at least one basic secondary amino radical and characterized byfreedom from any primary amino, radical; and (c) formaldehyde; saidcondensation reaction being conducted at a temperature above the boilingpoint of water and below 150 C., with vthe provisothat the condensationreaction be conducted so as toproduce a significant portion of theresultant in which each of the three reactants have contributed part ofthe ultimate molecule by virtue of a formaldehyde-derived methylenebridge connecting the amino nitrogen atom with a resin molecule; withthe added proviso that the molar ratio of reactants be approxirnately1,2 and 2, respectively; with the further proviso that said procedureinvolve the use of a solvent; and with the final proviso that theresinous condensation product resulting from the process be heat-stable.

9. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the gluconic acid salts of the basic products obtained in turnin the process of condensing (a) an oxyethylation-susceptible, fusible,

non-oxygenated organic solvent-soluble, water-insoluble,

low-stage phenol-formaldehyde resin having an average molecular weightcorresponding to at least 3 and not over 6 phenolic nuclei per resinmolecule; said resin being difunctional only in regard tomethylol-forming reactivity; said resin being derived by reactionbetween a difunctional monohydric phenol and formaldehyde; said resinbeing formed in the substantial absence of trifunctional phenols; saidphenol being of the formula in which R is an aliphatic hydrocarbonradical having at least 4 and not more than 14 carbon atoms andsubstituted in the para position; (b) cyclic amidines selected from theclass consisting of substituted imidazolines and substitutedtetrahydropyrimidines in which there is present at least one basicsecondary amino radical and characterized by freedom from any primaryamino radical; and (0) formaldehyde; said condensation reaction beingconducted at a temperature above the boiling point of water and belowC., with the proviso that the con densation reaction be conducted so asto produce a significant portion of the resultant in which each of thethree reactants have contributed par-t of the ultimate molecule byvirtue of a formaldehyde-derived methylene bridge to produce an emulsionwhen said xylene solution is shaken vigorously with 1 to 3 volumes ofwater.

11. The process of claim 2 with the proviso that the hydrophileproperties of the gluconic acid salt of the basic product in an equalweight of xylene are suflicient to produce an emulsion when said xylenesolution is shaken vigorously with 1 to 3 volumes of water.

12. The process of claim 3 with the proviso that the hydrophileproperties of the gluconic acid salt of the basic product in an equalweight of xylene are sufficient to produce an emulsion when said xylenesolution is shaken vigorously with 1 to 3 volumes of water.

13. The process of claim 4 with the proviso that the hydrophileproperties of the gluconic acid salt of the basic product in an equalweight of xylene are sufficient to produce an emulsion when said xylenesolution is shaken vigorously with l to 3 volumes of water.

14. The process of claim 5 with the proviso that the hydrophileproperties of the gluconic acid salt of the basic product in an equalweight of xylene are sufficient to produce an emulsion when said xylenesolution is shaken vigorously'with 1 to 3 volumes of water.

15. The process of claim 6 with the proviso that the hydrophileproperties of the gluconic acid salt of the basic product in an equalweight of xylene are sufl'icient to produce an emulsion when said xylenesolution is shaken vigorously with 1 to 3 volumes of water.

16. The process of claim 7 with the proviso that the hydrophileproperties of the gluconic acid salt of the basic product in an equalweight of xylene are suificient to produce an emulsion when said xylenesolution is shaken vigorously with 1 to 3 volumes of water.

17. The process of claim 8 with the proviso that the hydrophileproperties of the gluconic acid salt of the basic product in an equalweight of xylene are sufliicient to produce an emulsion when said xylenesolution is shaken vigorously with 1 to 3 volumes of water.

18. The process of claim 9 with the proviso that the hvdrophileproperties of the gluconic acid salt of the basic product in an equalweight of xylene are suficient to produce an emulsion when said xylenesolution is shaken vigorously with 1 to 3 volumes of water.

References Cited in the file of this patent UNITED STATES PATENTS2,031,557 Bruson Feb. 18, 1936 2,451,153 Charlton et a1 Oct. 12, 19482,456,357 Allen Dec. 14, 1948 2,457,634 Bond et a1 Dec. 28, 19482,542,001 De Groote et al Feb. 20, 1951 2,568,739 Kirkpatrick et alSept. 25, 1951 2,679,488 De Groote May 25, 1954

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPECHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIERINCLUDING THE GLUCONIC ACID SALTS OF THE BASIC PRODUCTS OBTAINED IN TURNIN THE PROCESS OF CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE,NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGEPHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDINGTO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAIDRESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY;SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRICPHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVETOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCEOF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA